title: Hypochlorite reacts with an organic hydroperoxide forming free radicals, but not singlet oxygen, and thus initiates lipid peroxidation.
abstract: The mechanism of the reaction of hypochlorite with t-butyl hydroperoxide as a model organic hydroperoxide was studied. The reaction produces chemiluminescence with rate constant 13 +/- 2 mM-1.sec-1. The chemiluminescence of this reaction was compared with that of the hypochlorite reaction with H2O2 where singlet oxygen (1O2) is formed. In the hypochlorite reaction with H2O2, the effect of hypochlorite concentration on the integrated chemiluminescence intensity is quadratic: a red filter with transmission > 600 nm did not significantly decrease the chemiluminescence intensity: substitution of D2O for H2O increased the luminescence intensity 10-fold; infrared monomol emission was observed at 1270 nm. These results confirm the formation of 1O2 during the hypochlorite reaction with H2O2. However, when t-butyl hydroperoxide was used instead of H2O2, the concentration effect significantly differed from quadratic, and the red filter decreased the luminescence intensity by approximately 99%; D2O slightly decreased the luminescence intensity. Finally, addition of t-butyl hydroperoxide to hypochlorite was not associated with monomol emission of 1O2 in the infrared region. The data exclude the possibility of singlet oxygen formation in the hypochlorite reaction with the organic hydroperoxide. According to 1H-NMR spectroscopy, di-t-butyl peroxide is the main product of the hypochlorite reaction with t-butyl hydroperoxide; its production can be explained by radical formation, i.e., by generation of t-butyloxy radical. t-Butyl hydroperoxide and cumene hydroperoxide promoted hypochlorite-induced lipid peroxidation of phospholipid liposomes. The free radical scavenger butylated hydroxytoluene completely inhibited this effect. The data suggest that organic hydroperoxides, always present in certain amounts in vivo, may be the intermediates that interact with hypochlorite-forming free radicals which are initiators of lipid peroxidation.
authors.affiliation: Institute of Physico-Chemical Medicine, Moscow, Russia. panasenko@glas.apc.org
authors.forename: O M
authors.initials: OM
authors.lastname: Panasenko
authors.forename: J
authors.initials: J
authors.lastname: Arnhold
authors.forename: J
authors.initials: J
authors.lastname: Schiller
mesh_terms: D005609:Free Radicals; D006861:Hydrogen Peroxide / Q000378:metabolism*; D006997:Hypochlorous Acid / Q000378:metabolism*; D007700:Kinetics; D015227:Lipid Peroxidation; D008163:Luminescent Measurements; D008956:Models, Chemical; D010100:Oxygen / Q000378:metabolism*; D010545:Peroxides / Q000378:metabolism; D010777:Photochemistry; D026082:Singlet Oxygen; D020122:tert-Butylhydroperoxide
chemical_list: D005609:Free Radicals; D010545:Peroxides; D026082:Singlet Oxygen; D006997:Hypochlorous Acid; D020122:tert-Butylhydroperoxide; D006861:Hydrogen Peroxide; D010100:Oxygen